Textile printing paste



inafter.

Patented Jan. 5, 1943 No Drawing. Application February 10, 1940, Serial No. 318,325

G'GIaims.

This invention relates to the art of printing textiles and more particularly relates to an improved textile printing paste containing an insoluble color pigment, to the method of applying the same to a fabric and to the improved printed fabric obtained.

It has heretofore been the practice in printing of insoluble coloring agents on textile fabricsto print The water-dn-oll type of cellulose ether emulsion which has been found to be useful in carrying out this invention will contain a water-insoluble cellulose ether, as, for example, ethyl cellulose, propyl cellulose, butyl cellulose, benzyl cellulose, mixed ethyl benzyl cellulose, mixed ethyl 1 butyl cellulose, etc. A water-in-oil type of mulsuch colors from a paste containing the coloring agent in a soluble form and developing the insoluble coloron the fabric by suitable after-treatment. Such printing pastes have contained as carriers or thickeners such materials as starch and gum tragacanth. After the paste has been applied to the fabric and the color has.beco me fixed or developed on the fabric by some suitable treatment, the fabric is subjected to a washing treatment to remove the starch or gum carrier.

The color developing or fixing op ration is a very delicate operation subject to a wide variability in the final result; Insumcient developing or over developing are common reasons for rejection of the printed goods. Also, many delicate fabrics do not satisfactorily withstand the rather severe washing treatment necessary to remove the starch or'gum carrier and thus give printed fabrics of weakened strength.

It is an object of this invention to overcome the above disadvantages in textile printing.

It is another object to provide a printing paste containing an insoluble color pigment.

It is a further object to provide a method of printing textile fabrics with a printing paste containing an insoluble color pigment which eliminates the developing and washing treatments necessary in using the prior art'printing pastes and methods.

It is a further object to provide a printed'textile fabric in which an insoluble color pigment is bonded to the fabric by means of a novel bondin material.

Other objects of the invention will appear here- The objects above may be accomplished in ac- 'cordance with this invention by the preparation of printing pastes containing an insoluble color pigment dispersed in a carrier vehicle comprising a water-in-oil emulsion of a water-insoluble cellulose ether. The printing paste so formed is then applied to a textile fabric andthe fabric dried.

Since the insoluble color pigment isin its fully devolped state, no treatment on .the fabric is sion of a cellulose ether is particularly useful in this invention because of the high viscosity which such emulsions possess with very low solids content.

'I'he water-in-oil type of cellulose ether emulsion utilized in this invention may be prepared by first emulsifying a water-immiscible solvent solution of the cellulose ether, carrying out the emulsiflcation in water with the aid of a suitable emulsifying agent. If desired, a plasticizer for the cellulose ether or a suitable synthetic resin, or both. may be included in the solvent solution of the cellulose ether. The oil-in-water type of emulsion formed in this manner may then be reversed to a water-in-oil type of emulsion. In this manner, the cellulose ether solution becomes the continu-.

ous phase of the emulsion. Alternatively, a waterin-oil emulsion of the cellulose ether may be prepared directly without-the intermediate preparation of the oil-in-water type of emulsion.

As plasticizers for the cellulose ether; a solid or a liquid plasticizer may be used. Suitable plasticizers are hydrogenated methyl abietate, hydrogenated ethyl abietate, triphenyl phosphate, tributyl phosphate, methylphthalylmethyl glycollate, ethylphthalylethyl glycollate, etc.

As a suitable resin for use with the cellulose ether, a resin which is compatible with the cellulose ether, is resistant'to alkalies and exerts a softening action on the cellulose ether may be used. By softening action, I mean a lowering of the melting point of the cellulose ether and not necessarily a plasticizing of the cellulose ether-- in the strict sense of the term. Thus, I have found that rosin modified alkyd resins, such as rosin modified or hydrogenated rosin modified terpene-maleio"anhydride resins, rosin modified maleate resins, drying oil modified terpene-maleic anhydride resins, polymerized hydrocarbon resins,

such x as polymerized napthalene, polymerized coumaroneindene, or hydrogenated forms thereof, 100% phenolic resins, polyhydric alcohol esters of hydrogenated rosin, as well as other types having the above defined properties, may be used with w the cellulose ether. 1

necessary to develop the color, the only treatment necessary being the drying of the fabric to remove water and volatile solvent from the emulsion.

As emulsifying agents for preparing the emulsion of the cellulose ether with or without'a plas- 55 ticizer and with or without asuitable resin,.I may employ, for example, the alkali metal salts of the higher aliphatic half ester sulfates, as sodium lauryl sulfate, sodium stearyl sulfate, etc; sulfonated oils, as sulfonated castor oil, sulfonated olive soil, etc; soaps, as sodium stearate, potassium oleate, sodium oleate, etc; alkali metal salts of alkyl naphthalene sulfonic acids, as sodium butyl naphthalene sulfonate, sodium isopropyl naphthalene sulfonate, etc.

The cellulose ether, together with the plasticizer and the resin, if either or both are employed, will preferably be dissolved in a suitable water-immiscible solvent mixture before emulsification and the solvent solution emulsified in water by means of the emulsifying agent. Suit able solvent mixtures may include solvents such as, forexample, light aromatic hydrocarbons, as,

for example, toluol, xylol, Hi-Flash naphtha, etc.; petroleum hydrocarbons as, for example, Stoddard solvent, Solvesso No. 2, Solvesso No. 3, etc.; butanol; pine oil, etc. By Stoddard solvent, Solvesso No. 2, and Solvesso No. 3 are meant the petroleum hydrocarbon solvents known in the industry by those names. They may be generally characterized as follows:

The oil-in-water type of emulsion obtained according to the above description may be reversed so as to form a water-in-oil type of emulsion by addition of a suitable reversing agent as, for example, aluminum stearate, acetic acid, a mixture of pine oil and acetic acid, or an alkali, as potassium or sodium hydroxide, or by any other suitable means. If it is desirable to. prepare a water-inoil type emulsion directly, this may be done, for example, by adding one of the above reversing agents to the solvent solution of the cellulose ether and emulsifying in water with an emulsifying agent.

A water-in-oil type emulsion may also be prepared directly by stirring water and a suitable solvent into a water-immiscible solvent solution of a water-insoluble cellulose ether containing an insoluble pigment in dispersed form, then homogenizing the resulting water-in-oil type emulsion in a suitable colloid mill or homogenizer. If desired, the pigment may be first dispersed in the water and the emulsion prepared as above.

The insoluble color pigments which constitute an essential component of the printing pastes described in accordance with this invention may be either the inorganic or the organic coloring materials which are insoluble in either water or oil and are commonly used inprinting pastes. The organic pigments are those which consist either wholly or in part of dyestuffs which have been rendered insoluble in water and oil. These include those organic pigments which are made by precipitation on a suitable base. These also include the dyes which have been precipitated or rendered water-insoluble by various precipitating means such as barium chloride, lead acetate, tartaric acid, aluminum hydrate, etc., as well as the insoluble lakes and azo and diazo colors. Some of the more common insoluble color P18- scribed in accordance with this invention are known to the trade under the following names:

Vulcan Fast Yellow 5G Vulcan Green BA extra Vulcan Fast Red B Pdr.

Vulcansol Blue G Pdr. fine Blue Lake (BM-201-D) Green Lake (GP-510-D) C. P. Chrome Yellow LM (65%) Monastral Green Toner pulp (GT-73-P) Monastral Blue Toner pulp (BT--P) C. P. Chrome Green Lt.

Ponsol Golden Orange G double paste (Color Index 1096) The printing pastes prepared and utilized in accordance with this invention may be prepared by mixing the insoluble color pigment such as described above into the water-in-oil emulsion of a water-insoluble cellulose ether to provide the improved printing paste. The body and thickness of the printing paste may be varied as desired by variation of the ingredients of the waterin-oil emulsion of the cellulose ether and by the amount of dissolved solids in the emulsion as well as by theamount of the solvent and by the amount of the color pigment added, and mixing the insoluble color pigment with the cellulose ether emulsion. It may be desirable inv some cases to include an auxiliary solvent, such as, for example, Stoddard solvent, Solvesso No. 2, pine oil, etc.

The solids content of the water-in-oil cellulose ether emulsion utilized in the printing paste will usually not be in excess of about 40% by weight and preferably will be within the range of about 1% to about 20%. The water-in-oil cellulose ether emulsion will be used in the printing paste usually in such an amount that the solids of the printing paste derived from the cellulose ether emulsion will not be in excess of about 10% of the total weight of the paste and preferably will be no more than about 6% of the total weight of the paste. The amount of insoluble color pigment included in the printing paste may be adjusted to provide the shade and quality of print desired and will depend to a large extent on the particular pigment employed, Generally speaking, the total solids content of the printing paste will not exceed about 20% by weight and preferably will be within the range of about 2% to about 15% by weight.

The method of applying a printing paste prepared in accordance with this invention to a textile fabric will involve the essential steps of applying the printing paste to the fabric by means of printing rollers or screens such as in screen printing followed by drying of the printed fabric in any suitable manner. The temperature of drying, for example, may be within the range of about 180 to about 320 F. and preferably may be within the range of about 220 to about 300 F. Developing of the color on the fabric or washing and soaping of the printed fabric are not necessary since development of the color is unnecessary and removal of the solids deposited from the cellulose ether emulsion is not desired and is not possible by washing and soap- 1 ing. The drying treatment to which the printed fabric is subjected merely removes the water and other volatile solvents contained "in the emulsion. 7

The printed fabric produced by printing a textile fabric with the printing paste described ments which may be used in printing pastes de- 75 above and according to the procedure described pastes.

above will be characterized as carrying in its printed areas an insoluble color pigment bonded to the fabric by means of the cellulose ether composition. Such cellulose ether composition may be a water-insoluble cellulose ether alone or mixed with either a plasticizer or a suitable synthetic resin, or both. The printed fabric is substantially resistant to crocking and is also resistant to laundering.

It will be further characterized by a uniformity of shade in the printed areas, and by a depth of shade which may be varied by the amount of color pigment incorporated into the printing paste.

The following examples illustrate the prepara ion of the improved printing pastes and the method of printing fabrics with such printing A solution of an ethyl cellulose composition was prepared containing the following ingredients:

' Parts by weight- 1 32 Ethylcellulose Trlphenyl phosphate 16 Glycerol ester of hydrogenated rosin 10 Xylol 106 Hi-Flash naphthanfl 20 Butanol 16 The above solution was then emulsified by 100 parts by weight of water containing 1.5 parts by weight of potassium oleate. To the oil-inwater emulsion obtained, 120 parts by weight of a 6% solution of aluminum stearate in pine oil and 1 parts by weight ofacetic acid were added. The mixture was stirred until a smooth water-inoil emulsion resulted. Various insoluble color pigments were then stirred into the water-in-oil ethyl cellulose emulsion together with additional water and Stoddard solvent to give a consistency suitable for printing. The proportions'of ingredients contained in the series of printing pastes the printed fabric was fast to crocking and was prepared with the. various color pigments are tabulated below in Table 1.

' Table 1 Water-in-oilethyl cellulose emulsion Vulcan Fast Yellow G.

Vulcan Green BA extra;

Vulcan Fast Red B powder Vulcansol Blue 201- GreenLake (GP- aterm. Stoddard solvent.

Each of the above printing a print 801: 80 print cloth and the cloth was then treatment over heated rolls subjected toa drying at a temperature of bout 260 F; In'each case,

Exurrnr II A solution of 22 parts by weight of ethyl cellulose in'150 parts by weight of xylol and 28 parts by weight of butanol was prepared. This solution was emulsified in 100 parts by weight of water containing 1.5 parts by weight of potassium oleate. To the oil-in-water emulsion obtained, 20 parts by weight of pine oil and .74 part by weight of acetic acid were added and the mixture stirred until a smooth water-in-oil emulsion resuited. The emulsion was further thinned with 130v parts by weight of Stoddard solvent. The

water-in-oil emulsion obtained had a solids con tent of 5.25% by weight. Four parts by weight of Monastral Blue Toner pulp BT-70-P were stirred into 30 parts by weight of the above waterin-oil emulsion and 46 parts by weight of waterand'20 parts by weight of Stoddard solvent added and the mixture stirred until a smooth paste resulted. The consistency of the paste was satis- .factory for printing. The printing paste obtained was used to print 80 x 80 print cloth. The printed cloth was dried over a series of heated rolls at a temperature of 260 F. Theprint obtained showed excellent bond to the fabric, was resistant to crocking and to laundering.

EXAMPLE III A solution of 32 parts by weight of ethyl cellulose and 10 parts of mineral oil in 120 parts by weight of xylol, 20 parts by weight of Hi-Flash naphthaand 18 parts by weight of butanol was prepared. This solution was emulsified with 100 parts by weight of water containing 1.5% by weight of potassium oleate. The oil-in-water emulsion obtained was reversed to a water-in-oil emulsion by addition of 20 parts by weight of pine oil and .75 part by weight of acetic acid and the emulsion thinned further with 130 parts by weight of Stoddard solvent. The resulting water-in-oil emulsion had a solids content of 7.45% by weight. Four parts by weight of Green Lake (GP-510-D) were then stirred into 30 parts by weight of the water-in-oil emulsion prepared above and 46 parts by weight of water and 20 parts by weight pastes were used to of Stoddard solvent stirred into the mixture until it became smooth. The paste resulting had a consistency suitable for printing. An x 80 print cloth was printed with the paste, and the cloth dried over a series of heated rolls at a temperature of 260 F. The print obtained was securely bonded to the fabric and was resistant to crocking and laundering. 1

EXAMPLE IV A solution of 32 parts by weight of ethyl cellulose and 10 parts by weight of the diethylene glycol ester of hydrogenated rosin in parts by weight of xylol, 20 parts by weight of Hi-flash naphtha and 18 parts by weight ofbutanol was prepared. This solution, was then emulsified with 100 parts by weight of water containing 1.5% by weight of potassium oleate. emulsion obtained was reversed to a water-in-oil emulsion by addition of 20 parts by weight of pine oil and .75 partby weight of acetic acid. The mixture was stirred and parts by weight of Stoddard solvent-added to reduce the viscosity. The resulting water-in-oil emulsion contained 9.65% by weight of solids; Four parts by weight 0! C. P. Chrome Yellow LM (65%) were then stirred into 30 parts by weight of the above water- The oil-in-water;

EXAMPLE V A solution of 32 parts by weight of ethyl cellulose, 26 parts by weight of 2. glycerol ester of hydrogenated rosin, 106 parts by weight of xylol, parts by weight of Hi-Flash naphtha, 16

parts by weight of butanol, 20 parts by weight of pine oil, and 130 parts by weight of Stoddard solvent was prepared. The resulting solution contained 16.5% solids. An oil-in-water emulsion was prepared by mixing together 35 parts by weight of the above solution with 21 parts by weight of Solvesso No. 2 and 1 part by weight of acetic acid, to which was added with stirring 43 parts by weight of water. The resulting water-in-oil emulsion was then passed through a homogenizer. A printing paste was prepared by mixing together 50 parts by weight of the above emulsion and 12 parts by weight of Solvesso No. 2 to which was added with stirring 32 parts by weight of water in which was dispersed 4 parts by weight of Monastral Blue Toner pulp BT-70-P- After mixing, the printing paste was homogenized and used to print on 80 x 80 print cloth, and the cloth then subjected to a drying treatment over heated rolls at a temperature of about 260 F. The print exihibited substantial fastness to washing and crocking.

The printing pastes described above present several important advantages in the art of printing textiles over the printing pastes heretofore used. By printing with a paste containing an insoluble pigment, a greatly simplified printing procedure may be used. Thus, the steam and aging treatments required with use of prior printing pastes and also the washing and soaping treatments to remove the starch or gum carrier may be dispensed with, since with use of pigment no fixing or developing of the color on the fabric is necessary. The normal variations due to insufllcient developing or to over-developing are not encountered. A color uniformity of shade is, therefore, obtained with a minimum of variation. Also, the printed fabrics obtained in accordance with this invention exhibit a very satisfactory bonding of the pigment color to the cloth without materially altering the stifiness of the printed fabric in the printed areas. The elimination of the severe washing treatment usually given to printed fabrics to remove the starch or gum carrier makes it possible to provide delicate printed fabrics with their original strength.

It will be understood that the details and examples given hereinbefore are illustrative only and that the invention as broadly described and claimed is in no way limited thereby.

What I claim and desire to protect by Letters Patent is:

1. A textile printing paste having a total solids content not in excess of about 20 per cent by weight comprising an insoluble color pigment dispersed in an emulsion comprising a continuous phase consisting essentially of a solution of a water-insoluble cellulose ether composition in a volatile water-immiscible organic solvent and a discontinuous aqueous phase, the solids content of the said paste derived from the emulsion not exceeding about 10 per cent by weight.

2. A textile printing paste having a total solids content not in excess of about 20 per cent by weight comprising an insoluble color pigment dispersed in an emulsion comprising a continuous phase consisting essentially of a solution of an ethyl cellulose composition in a volatile waterimmiscible organic solvent and a discontinuous aqueous phase, the solids content of the said paste derived from the emulsion not exceeding about 10 per cent by weight.

3. A textile printing paste having a total solids content not in excess of about 20 per cent by weight comprising an insoluble color pigment dispersed in an emulsion comprising a continuous phase consisting essentially of a solution of a plasticized ethyl cellulose composition in a vole tile water-immiscible organic solvent and a discontinuous aqueous phase, the solids content of the said paste derived from the emulsion not exceeding about 10 per cent by weight.

4. A textile printing paste having a total solids content within the range of about 2 per cent to about 15 per cent by weight comprising an in soluble color pigment dispersed in an emulsion comprising a continuous phase consisting essentially of a; solution of an ethyl cellulose composition in a volatile water-immiscible organic solvent and a discontinuous aqueous phase, the solids content of the said paste derived from the emulsion not exceeding about 6 per cent by weight.

5. A textile printing paste having a total solids content not in excess of about 20% by weight comprising an insoluble color pigment dispersed in an emulsion comprising a continuous phase consisting essentially of a solution in a volatile water-immiscible organic solvent of an ethyl cellulose composition containing a resin which is compatible with the ethyl cellulose, is resistant to alkalies, and which exerts a softening action on the ethyl cellulose, and a discontinuous aqueous phase, the solids content of the said paste derived from the emulsion not exceeding about 10% by weight.

6. A textile printing paste having a total solids content not in excess of about 20% by weight comprising an insoluble color pigment dispersed in an emulsion comprising a continuous phase consisting essentially of a solution in a volatile water-immiscible organic solvent of an ethyl cellulose composition containing a polyhydric alcohol ester of a hydrogenated rosin, and a discontinuous aqueous phase, the solids content of the said paste derived from the emulsion not exceeding about 10% by weight.

LOUIS E. ANDERSON, JR. 

